JP2016175213A - Composition liquid for three-dimensional molding and three-dimensional molding material set, and method and apparatus for manufacturing three-dimensional molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition liquid for three-dimensional molding which is excellent in storage stability, and can manufacture a three-dimensional molding having a complicated shape with high dimensional accuracy and such a strength as to prevent the three-dimensional molding from losing forms before sintering and the like.SOLUTION: A composition liquid for three-dimensional molding which is used for forming a three-dimensional molding that is formed of a powder material for three-dimensional molding containing an organic material and a base material contains a crosslinking agent crosslinked with the organic material, and a water-soluble resin having a weight average molecular weight of 50,000 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a three-dimensional modeling composition liquid, a three-dimensional modeling material set, and a three-dimensional model manufacturing method and manufacturing apparatus.

Recently, there is an increasing need for low-lot production of complex and fine three-dimensional objects. As a technique for meeting this need, a powder bonding method has been proposed.
As this powder bonding method, for example, a method of supplying an adhesive material to a thin powder layer using an inkjet method, or a method of laminating a powder material in which powder particles and adhesive particles are mixed and applying a binder is provided. A method of producing a three-dimensional structure by dissolving and solidifying adhesive material particles (see Patent Document 1), a powder material obtained by coating a base material such as glass or ceramic with a hydrophobic resin, such as limonene or toluene A method for producing a three-dimensional structure by dissolving a coating resin with a solvent to produce a three-dimensional structure (see Patent Document 2) has been proposed.

  However, the technique described in Patent Document 1 has sufficient strength for a three-dimensional structure because the dissolved adhesive liquid does not spread evenly between the powder particles even when the binder material is applied and the adhesive particles are dissolved. It is difficult to give accuracy. In addition, when the adhesive material is supplied by an ink jet method, there is a problem that the nozzle head to be used is clogged, the selection of the adhesive material that can be used is restricted, the cost is high, and it is not efficient.

  Further, in the technique described in Patent Document 2, limonene is low in volatility and tends to remain on a three-dimensional structure and may cause a decrease in strength. Furthermore, a low-volatile solvent such as toluene has a safety problem.

  Therefore, the present invention provides a composition solution for three-dimensional modeling that can produce a three-dimensional structure having excellent storage stability and a complicated shape with sufficient dimensional accuracy and sufficient strength that does not cause deformation before sintering. The purpose is to do.

  The three-dimensional modeling composition liquid of the present invention as a means for solving the above problems is a three-dimensional modeling composition liquid used for forming a three-dimensional modeling object composed of a three-dimensional modeling powder material including an organic material and a base material. And a water-soluble resin having a weight average molecular weight of 50,000 or more.

  According to the present invention, there is provided a three-dimensional composition liquid that is excellent in storage stability and capable of producing a three-dimensional structure having a complicated shape with sufficient dimensional accuracy and sufficient strength that does not cause deformation before sintering or the like. be able to.

FIG. 1 is a schematic view showing an example of a powder additive manufacturing apparatus of the present invention. FIG. 2 is a schematic view showing another example of the powder additive manufacturing apparatus of the present invention.

(3D modeling liquid)
The composition solution for three-dimensional modeling of the present invention is used for forming a three-dimensional modeled object composed of a powder material for three-dimensional modeling including an organic material and a base material, a crosslinking agent that crosslinks with the organic material, and a weight average molecular weight. And 50,000 or more of a water-soluble resin, and preferably contains a stabilizer and a solvent, and further contains other components as necessary.

  The three-dimensional modeling composition liquid is used to cure the three-dimensional modeling powder material. The “curing” means a state in which the base materials are fixed or agglomerated with each other through an organic material, and the three-dimensional modeling powder material can maintain a certain three-dimensional shape by the curing.

  When the three-dimensional modeling composition liquid is applied to the organic material included in the three-dimensional modeling powder material, the organic material is dissolved by the solvent contained in the three-dimensional modeling composition liquid, and the three-dimensional modeling composition liquid is used. Are cross-linked by the action of the cross-linking agent contained in.

-Water-soluble resin-
The water-soluble resin is not particularly limited as long as the weight average molecular weight is 50,000 or more, and can be appropriately selected according to the purpose. Polyvinyl pyrrolidone (PVP), polyethylene glycol and the like are preferable, and polyvinyl pyrrolidone is preferable. Particularly preferred.

The polyvinyl pyrrolidone is a water-soluble polymer, and there is an example in which the conventional water-based recording ink containing a pigment as a colorant is used as a dispersant for dispersing the pigment.
In the composition liquid for three-dimensional modeling of the present invention, there is no need for pigment dispersion, and the purpose is to provide excellent adhesion to the polyvinyl pyrrolidone base material such as metal or ceramic, and storage stability of the three-dimensional modeling composition liquid. Contained as. In particular, when a three-dimensional model is manufactured using a base material having a high specific gravity such as metal, the strength of the adhesion of polyvinylpyrrolidone is very effective in maintaining the shape of the three-dimensional model.

The water-soluble resin has a weight average molecular weight of 50,000 or more, preferably 700,000 or more. When a water-soluble resin having a weight average molecular weight of 50,000 or more is used, and the three-dimensional modeling composition liquid is applied and dissolved in the organic material, the three-dimensional modeling composition liquid is applied and dissolved in the three-dimensional modeling. The strength after solidification of the mixture with the water-soluble resin in the composition liquid for use is sufficient to maintain the shape of the three-dimensional structure. Furthermore, when the water-soluble resin having a weight average molecular weight of 700,000 or more is used, the three-dimensional object can be formed even if the addition amount is reduced as compared with the case where the water-soluble resin having a weight average molecular weight of less than 700,000 is used. It will be sufficient to maintain the shape.
The weight average molecular weight of the water-soluble resin can be calculated based on, for example, a molecular weight distribution of the isolated water-soluble resin obtained by gel permeation chromatography (GPC).

  The content of the water-soluble resin is not particularly limited and may be appropriately selected depending on the purpose. It is preferably 0.1% by mass to 5% by mass with respect to the total amount of the three-dimensional modeling composition liquid. . In the preferable numerical range of the content, the adhesion to a base material such as metal is improved, and the storage stability of the three-dimensional modeling composition liquid is improved.

-Solvent-
The solvent is not particularly limited as long as it can dissolve the organic material contained in the three-dimensional modeling powder material, and can be appropriately selected according to the purpose. Examples thereof include water and organic solvents. . These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said water, According to the objective, it can select suitably, For example, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water etc. are mentioned. It is done.
The content of the water in the three-dimensional modeling composition liquid is preferably 40% by mass or more and 95% by mass or less, and more preferably 50% by mass or more and 85% by mass or less. When the water content is 40% by mass or more, when a water-soluble polymer is used as the organic material of the three-dimensional modeling powder material, the water-soluble polymer can be sufficiently dissolved, and the strength of the cured product is improved. To do. Further, when the water content is 95% by mass or less, drying of the ink jet nozzle can be prevented during standby, and nozzle missing does not occur.

The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanol, 1,2,6-hexanetriol, 1,2-butanediol, 1,2-hexanediol, 1 , 2-pentanediol, 1,3-dimethyl-2-imidazolidinone, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 2,2-dimethyl-1,3-propanediol, 2,3-butanediol, 2,4-pentanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2- Pyrrolidone, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 3-methyl- , 3-hexanediol, N-methyl-2-pyrrolidone, N-methylpyrrolidinone, β-butoxy-N, N-dimethylpropionamide, β-methoxy-N, N-dimethylpropionamide, γ-butyrolactone, ε-caprolactam , Ethylene glycol, ethylene glycol-n-butyl ether, ethylene glycol-n-propyl ether, ethylene glycol phenyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoethyl ether, glycerin, diethylene glycol, diethylene glycol-n-hexyl ether, Diethylene glycol methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether Ter, diglycerin, dipropylene glycol, dipropylene glycol n-propyl ether, dipropylene glycol monomethyl ether, dimethyl sulfoxide, sulfolane, thiodiglycol, tetraethylene glycol, triethylene glycol, triethylene glycol ethyl ether, triethylene glycol dimethyl ether , Triethylene glycol monobutyl ether, triethylene glycol methyl ether, tripropylene glycol, tripropylene glycol-n-propyl ether, tripropylene glycol methyl ether, trimethylol ethane, trimethylol propane, propyl propylene diglycol, propylene glycol, propylene glycol -N-butyl ether, propylene glycol t-butyl ether, propylene glycol phenyl ether, propylene glycol monoethyl ether, hexylene glycol, polyethylene glycol, polypropylene glycol, aliphatic solvents, ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, ethers such as glycol ether System solvents and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, alcohol such as ethanol, ether solvents, ketone solvents, etc. from the viewpoint of discharge stability (less change in viscosity over time) when applying the environmental load and the composition liquid for three-dimensional modeling by the ink jet method Aqueous solvents are preferred.
Moreover, it is preferable to use the organic solvent whose vapor pressure in 100 degreeC is 10 mmHg or more from the point which the drying property after three-dimensional modeling is favorable and the intensity | strength of a three-dimensional molded item (hardened | cured material) improves. Examples of the organic solvent having a vapor pressure of 10 mmHg or higher at 100 ° C. include 3-methyl-1,3-butanediol, propylene glycol, 2,3-butanediol, 1,2-butanediol, and 1,3-butane. Examples include diols.

  The content of the organic solvent is not particularly limited and can be appropriately selected in consideration of blending components such as a cross-linking agent, applicability and handleability of a three-dimensional modeling composition liquid, and productivity of a three-dimensional model. 1 mass% or more and 50 mass% or less are preferable with respect to the whole quantity of the said composition liquid for three-dimensional modeling, and 10 mass% or more and 40 mass% or less are more preferable. When the content is 1% by mass or more, the moisture retention of the three-dimensional modeling composition liquid is appropriate, drying of the inkjet nozzle during standby can be prevented, and nozzle missing does not occur. Further, when the content is 50% by mass or less, the viscosity of the composition liquid for three-dimensional modeling becomes appropriate, the discharge stability is good, and it is easy to dry after three-dimensional modeling, and the three-dimensional modeled product (cured product). The strength of is improved.

-Crosslinking agent-
The cross-linking agent is not particularly limited as long as it has a property capable of cross-linking the organic material contained in the three-dimensional modeling powder material, and can be appropriately selected according to the purpose. For example, metal salt, metal A complex, an organic zirconium compound, an organic titanium compound, a chelating agent, and the like can be given.
Examples of the organic zirconium compound include zirconium oxychloride, ammonium zirconium carbonate, zirconium ammonium lactate and the like.
Examples of the organic titanium compound include titanium acylate and titanium alkoxide.
These may be used individually by 1 type and may use 2 or more types together. Among these, metal salts are more preferable.

Suitable examples of the metal salt include those that ionize a divalent or higher valent metal in water. Specific examples of the metal salt include zirconium oxychloride octahydrate (tetravalent), aluminum hydroxide (trivalent), magnesium hydroxide (divalent), titanium lactate ammonium salt (tetravalent), basic aluminum acetate (Trivalent), zirconium carbonate ammonium salt (tetravalent), titanium triethanolamate (tetravalent), glyoxylate, zirconium lactate ammonium salt and the like are preferable. Among these, a zirconium compound is preferable, and ammonium zirconium carbonate is particularly preferable because the strength of the three-dimensional structure to be obtained is excellent.
Moreover, these can use a commercial item, As this commercial item, for example, a zirconium oxychloride octahydrate (Daiichi Rare Element Chemical Co., Ltd. product, zirconium oxychloride), aluminum hydroxide (Wako Pure) Yaku Kogyo Co., Ltd.), Magnesium Hydroxide (Wako Pure Chemical Industries, Ltd.), Titanium Lactate Ammonium Salt (Matsumoto Fine Chemical Co., Ltd., Orugatix TC-300), Zirconium Lactate Ammonium Salt (Matsumoto Fine Chemical Co., Ltd., Olga) Chicks ZC-300), basic aluminum acetate (manufactured by Wako Pure Chemical Industries, Ltd.), bisvinylsulfone compound (manufactured by Fuji Fine Chemical Co., Ltd., VS-B (K-FJC)), zirconium carbonate ammonium salt (first rare element) Chemical Industry Co., Ltd., Zircosol AC-20) Titanium triethanolaminate (manufactured by Matsumoto Fine Chemical Co., Ltd., ORGATICS TC-400), glyoxylate (Safelink SPM-01, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), adipic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd.), etc. It is done.

  The “crosslinking agent” in the present invention is a compound having a site capable of undergoing a crosslinking reaction with a functional group of an object to be crosslinked (organic material such as a polymer). It becomes a component of the binding site. Therefore, for example, like radicals (organic peroxides) and reducing substances, they generate free radicals when they themselves decompose by heat and light, add them to unsaturated monomers, and open double bonds. At the same time, a new radical reaction is generated and the process is repeated to accelerate the polymerization, or the hydrogen bonded to the carbon of the saturated compound is extracted to generate a new radical and the generated radicals are regenerated. It is a concept different from what is called an “initiator” for initiating or accelerating a radical reaction, which is not a constituent element of a cross-linking site, such as forming a bridge between saturated compounds by bonding. There is a clear distinction from the “crosslinking agent” in the present invention.

-Stabilizer-
The three-dimensional modeling composition liquid may cause a significant change in viscosity depending on the type and combination of the solvent and the cross-linking agent and storage conditions, and storage stability in consideration of summer use and storage is required.
In particular, the composition liquid for three-dimensional modeling using a zirconium carbonate ammonium salt, which is a cross-linking agent excellent in the strength of a three-dimensional model, tends to change in viscosity during storage, and the strength of the three-dimensional model and the three-dimensional model The stabilizer is an important additive in order to achieve both the storage stability of the composition liquid.

  The stabilizer is not particularly limited as long as it has the property of suppressing the viscosity change of the three-dimensional composition liquid and maintaining the storage stability, and can be appropriately selected according to the purpose. Preference is given to at least one compound selected from amino group-containing compounds, phosphono group-containing compounds, and gluconic acid and its salts.

As the amino group-containing compound, any of an amino group-containing polyhydric alcohol, a hydroxyl group-containing amine compound, and an amino group-containing chelating agent is preferable.
The amino group-containing polyhydric alcohol is preferably a dihydric alcohol or a trihydric alcohol. For example, 2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-ethyl-1,3 -Propanediol (AEPD), 2-dimethylamino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol (AHMPD) and the like.
Examples of the hydroxyl group-containing amine compound include triethanolamine.
Examples of the amino group-containing chelating agent include dihydroxyethylglycine (DHEG) or a salt thereof.
Examples of the phosphono group-containing chelating agent include amino trimethylene phosphonic acid (NTMP) or a salt thereof, phosphonobutanetricarboxylic acid (PBTC) or a salt thereof, hydroxyethane disulfonic acid (HEPD), or a salt thereof. It is done.
Examples of the gluconic acid or a salt thereof include gluconic acid and sodium gluconate.
Among the stabilizers, sodium gluconate, 2-amino-2-ethyl-1,3-propanediol (AEPD), dihydroxy from the viewpoint of the strength of the three-dimensional structure and the storage stability of the three-dimensional composition liquid. Ethylglycine salt and triethanolamine are preferable, and 2-amino-2-ethyl-1,3-propanediol (AEPD) is more preferable.

The content of the stabilizer is not particularly limited and can be appropriately selected according to the type, content, and other components of the crosslinking agent contained in the three-dimensional modeling composition liquid. 0.1 mass% or more and 5 mass% or less are preferable with respect to the whole quantity of a composition liquid.
When the content is within the preferable numerical range, the viscosity change of the three-dimensional modeling composition liquid can be suppressed and the storage stability can be maintained.

<Other ingredients>
As said other component, additives, such as surfactant, an antifoamer, a pH adjuster, antiseptic / antifungal agent, a chelating agent, a rust preventive agent, can be further added as needed.

-Viscosity change rate-
The three-dimensional modeling composition liquid preferably has a viscosity change rate of less than 20% before and after being left at 50 ° C. for 30 days, more preferably less than 10%, and even more preferably less than 5%.
When the viscosity change rate is less than 20%, the storage stability of the three-dimensional modeling composition liquid is appropriate. For example, when the three-dimensional modeling composition liquid is applied by an inkjet method, the ejection stability is high. As a result, a three-dimensional object having a complicated shape can be manufactured with sufficient dimensional accuracy and sufficient strength.

The rate of change in viscosity before and after being allowed to stand at 50 ° C. for 30 days can be measured as follows.
Viscosity measurement after putting the composition liquid for three-dimensional modeling into a polypropylene wide-mouth bottle (50 mL), leaving it in a thermostatic bath at 50 ° C. for 30 days, taking it out of the thermostatic bath and leaving it to room temperature (25 ° C.) I do. The viscosity of the three-dimensional modeling composition liquid before being put into the thermostat is set as the viscosity before storage, and the viscosity of the three-dimensional modeling composition liquid after being taken out of the thermostat is set as the viscosity after storage, and the viscosity change rate is calculated by the following formula. The pre-storage viscosity and the post-storage viscosity can be measured at 25 ° C. using an R-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
Viscosity change rate (%) = [(viscosity after storage) − (viscosity before storage)] / (viscosity before storage) × 100

The viscosity before storage of the three-dimensional modeling composition liquid is 25 ° C., preferably 25 mPa · s or less, more preferably 3 mPa · s or more and 20 mPa · s or less, and further preferably 3 mPa · s or more and 10 mPa · s or less. When the viscosity is 25 mPa · s or less, ejection from an inkjet nozzle is stabilized, and the strength of a cured product formed by applying the three-dimensional modeling composition liquid to the three-dimensional modeling powder material layer is sufficiently obtained. The dimensional accuracy is good.
The viscosity of the composition for three-dimensional modeling after storage is preferably 3 mPa · s or more and 10 mPa · s or less at 25 ° C.

-Surface tension-
The surface tension of the composition liquid for three-dimensional modeling is 25 ° C., preferably 40 N / m or less, and more preferably 10 N / m or more and 30 N / m or less. When the surface tension is 40 N / m or less, ejection from an inkjet nozzle is stabilized, and the strength of a cured product formed by applying the three-dimensional modeling composition liquid to the three-dimensional modeling powder material layer is sufficiently obtained. And dimensional accuracy is good.
The surface tension can be measured by, for example, DY-300 manufactured by Kyowa Interface Science Co., Ltd.

The three-dimensional modeling composition liquid is preferably alkaline, and the pH is more preferably 8-10.
The pH can be measured using, for example, a pH meter (HM30R, manufactured by Toa DKK Corporation).

  The composition solution for three-dimensional modeling of the present invention is excellent in storage stability and can be suitably used for simple and efficient production of various three-dimensional models, and the three-dimensional modeling material set of the present invention described later and the three-dimensional model of the present invention. It can use especially suitably for the manufacturing method of a modeling thing, and the manufacturing apparatus of a three-dimensional modeling thing.

(3D modeling material set)
The three-dimensional modeling material set of the present invention includes the three-dimensional modeling powder material and the three-dimensional modeling composition liquid of the present invention, and further includes other components as necessary.

As described above, the composition solution for three-dimensional modeling of the present invention contains the crosslinking agent and the water-soluble resin, preferably contains the stabilizer and the solvent, and further contains other components as necessary. It contains.
In the three-dimensional modeling material set of the present invention, the crosslinking agent may be included in a solid form instead of the solvent, or may be a set prepared by mixing with a solvent at the time of use.

<Powder material for three-dimensional modeling>
The three-dimensional modeling powder material includes a base material and an organic material, and preferably includes a base material coated with an organic material, and further includes other components as necessary.

-Base material-
The substrate is not particularly limited as long as it has a powder or particle form, and can be appropriately selected according to the purpose. Examples of the material include metals, ceramics, carbon, polymers, wood, and biocompatible materials. , Sand and the like. Among these, metals and ceramics that can be finally sintered are preferable from the viewpoint of obtaining a high-strength three-dimensional model.
The base material preferably does not react with the three-dimensional modeling composition liquid. Here, the reaction means various chemical reactions such as a crosslinking reaction, a covalent bond, and an ionic bond.
As said metal, stainless steel (SUS) steel, iron, copper, titanium, silver etc. are mentioned suitably, for example, As this stainless steel (SUS) steel, SUS316L etc. are mentioned, for example.
Examples of the ceramics include metal oxides, and specific examples include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), and the like.
Examples of the carbon include graphite, graphene, carbon nanotube, carbon nanohorn, and fullerene.
Examples of the polymer include known resins that are insoluble in water.
Examples of the wood include wood chips and cellulose.
Examples of the biocompatible material include polylactic acid and calcium phosphate.
These materials may be used alone or in combination of two or more.

In the present invention, commercially available particles or powders formed of these materials can be used as the substrate.
Examples of the commercial products include SUS316L (manufactured by Sanyo Special Steel Co., Ltd., PSS316L), SiO ₂ (manufactured by Tokuyama Co., Ltd., Excelica SE-15), Al ₂ O ₃ (manufactured by Daimei Chemical Co., Ltd., Tymicron TM-). 5D), ZrO ₂ (manufactured by Tosoh Corporation, TZ-B53) and the like.
The base material may be subjected to a known surface (modification) treatment for the purpose of increasing the affinity with the organic material.

The volume average particle size of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 0.1 μm or more and 500 μm or less, more preferably 5 μm or more and 300 μm or less, and 15 μm or more and 250 μm or less. Is more preferable.
When the volume average particle size is 0.1 μm or more and 500 μm or less, the manufacturing efficiency of the three-dimensional structure is excellent, and the handleability and handling properties are good. When the average particle size is 500 μm or less, when a thin layer is formed using the three-dimensional modeling powder material, the filling rate of the three-dimensional modeling powder material in the thin layer is improved, and the three-dimensional modeling obtained It is difficult for voids to occur in objects.
The volume average particle size of the substrate can be measured according to a known method using a known particle size measuring device such as Microtrac HRA (manufactured by Nikkiso Co., Ltd.).
There is no restriction | limiting in particular as particle size distribution of the said base material, According to the objective, it can select suitably.

  About the external shape, surface area, circularity, fluidity | liquidity, wettability, etc. of the said base material, it can select suitably according to the objective.

-Organic materials-
The organic material is not particularly limited as long as it dissolves in the three-dimensional modeling composition liquid and has a property capable of being crosslinked by the action of a crosslinking agent contained in the composition liquid.
In the present invention, the solubility of the organic material is such that, for example, when 1 g of the organic material is mixed and stirred in 100 g of the solvent constituting the three-dimensional composition liquid at 30 ° C., 90% by mass or more thereof dissolves. means.
As the organic material, the viscosity at 20 ° C. of a 4 mass% (w / w%) solution thereof is preferably 40 mPa · s or less, more preferably 1 mPa · s to 35 mPa · s, and more preferably 5 mPa · s to 30 mPa · s. The following are particularly preferred:
When the viscosity is 40 mPa · s or less, the strength of the cured product (three-dimensional modeled object) by the three-dimensional modeled powder material (layer) formed by applying the composition liquid to the three-dimensional model powder material is improved. Further, problems such as loss of shape are less likely to occur during subsequent processing or handling such as sintering. Moreover, it exists in the tendency which the dimensional accuracy of the three-dimensional molded item by the three-dimensional molded item powder material (layer) formed by giving the said composition liquid to the said three-dimensional molded powder material improves.
The viscosity can be measured according to, for example, JIS K7117.

The organic material is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferably water-soluble from the viewpoints of handleability and environmental load, and examples thereof include water-soluble resins and water-soluble prepolymers. , Etc. For a three-dimensional modeling powder material employing such a water-soluble organic material, water or an organic solvent can be used as a solvent for the three-dimensional modeling composition liquid, and when the powder material is discarded and recycled. It is also easy to separate the organic material and the substrate by water treatment.
Examples of the water-soluble resin include polyvinyl alcohol resin, polyacrylic acid resin, cellulose resin, starch, gelatin, vinyl resin, amide resin, imide resin, acrylic resin, and polyethylene glycol.
These may be homopolymers (homopolymers) or heteropolymers (copolymers) as long as they exhibit the above-mentioned water solubility, may be modified, are publicly known A functional group may be introduced or may be in the form of a salt.
Therefore, for example, the polyvinyl alcohol resin may be polyvinyl alcohol, or modified polyvinyl alcohol (acetoacetyl group-modified polyvinyl alcohol, acetyl group-modified polyvinyl alcohol, silicone-modified with acetoacetyl group, acetyl group, silicone, etc.) Polyvinyl alcohol, etc.), butanediol vinyl alcohol copolymer, and the like. Moreover, if it is the said polyacrylic acid resin, polyacrylic acid may be sufficient and salts, such as sodium polyacrylate, may be sufficient. If it is the said cellulose resin, a cellulose, carboxymethylcellulose (CMC), etc. may be sufficient, for example. Moreover, if it is the said acrylic resin, polyacrylic acid, an acrylic acid / maleic anhydride copolymer, etc. may be sufficient, for example.
Examples of the water-soluble prepolymer include an adhesive water-soluble isocyanate prepolymer contained in a water-stopping agent and the like.

  Examples of organic materials and resins other than water-soluble materials include acrylic, maleic acid, silicone, butyral, polyester, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polyethylene, polypropylene, polyacetal, and ethylene / vinyl acetate copolymer. , Ethylene / (meth) acrylic acid copolymer, α-olefin / maleic anhydride copolymer, esterified product of α-olefin / maleic anhydride copolymer, polystyrene, poly (meth) acrylic acid ester, α -Olefin / maleic anhydride / vinyl group-containing monomer copolymer, styrene / maleic anhydride copolymer, styrene / (meth) acrylic ester copolymer, polyamide, epoxy resin, xylene resin, ketone resin, petroleum resin, Rosin or its derivatives, coumarone indene resin, terpene tree , Polyurethane resin, styrene / butadiene rubber, polyvinyl butyral, nitrile rubber, acrylic rubber, synthetic rubbers such as ethylene / propylene rubber, nitrocellulose, and the like.

In the present invention, among the organic materials, those having a crosslinkable functional group are preferable. The crosslinkable functional group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydroxyl group, a carboxyl group, an amide group, a phosphate group, a thiol group, an acetoacetyl group, and an ether bond. Can be mentioned.
It is preferable that the organic material has the crosslinkable functional group in that the organic material can be easily crosslinked to form a cured product (three-dimensional modeled product). Furthermore, as described above, modified polyvinyl alcohol in which a crosslinkable functional group is introduced into the molecule is preferable. In particular, acetoacetyl group-modified polyvinyl alcohol is preferred. For example, when the polyvinyl alcohol has the acetoacetyl group, the acetoacetyl group is mediated by the metal in the crosslinking agent contained in the composition liquid. In addition, a complicated three-dimensional network structure (crosslinked structure) can be easily formed (excellent in crosslinking reactivity), and the strength is extremely excellent.
As said acetoacetyl group modified polyvinyl alcohol, what differs in characteristics, such as a viscosity and a saponification degree, may be used individually by 1 type, and may use 2 or more types together. It is more preferable to use an acetoacetyl group-modified polyvinyl alcohol resin having an average degree of polymerization of 400 to 1,100.

As said organic material, 1 type may be used individually, 2 or more types may be used together, and what was synthesize | combined suitably may be sufficient and a commercial item may be sufficient.
Examples of the commercially available products include polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-205C, PVA-220C), polyacrylic acid (manufactured by Toagosei Co., Ltd., Jurimer AC-10), and sodium polyacrylate (Toagosei Co., Ltd.). Manufactured by Jurimer AC-103P), acetoacetyl group-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gohsenx Z-300, Gohsenx Z-100, Gohsenx Z-200, Gohsenx Z-205, Gohsenx Z-210, Gohsenx Z) -220), carboxy group-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gosennex T-330, Gosennex T-350, Gosennex T-330T), butanediol vinyl alcohol copolymer (Nippon Synthetic Chemical) Nichigo G-Polymer OKS-8041), Carboxymethylcellulose (Daiichi Kogyo Co., Ltd., Serogen 5A), Starch (Sanwa Starch Co., Ltd., Hystad PSS-5), Gelatin (Nitta Gelatin Co., Ltd.) Company-made, B-matrix gelatin).

The coating thickness of the substrate with the organic material is preferably 5 nm or more and 1,000 nm or less, more preferably 5 nm or more and 500 nm or less, still more preferably 50 nm or more and 300 nm or less, and particularly preferably 100 nm or more and 200 nm or less.
In the present invention, since the curing action by the crosslinking agent is utilized, the coating thickness can be made smaller than that of the conventional one, and both strength and accuracy can be achieved even with a thin film.
When the average thickness as the coating thickness is 5 nm or more, the strength of the cured product (three-dimensional model) by the three-dimensional model powder material (layer) formed by applying the composition liquid to the three-dimensional model powder material 3D formed by applying the composition liquid to the three-dimensional modeling powder material so that there is no problem such as loss of shape during subsequent processing such as sintering or handling. The dimensional accuracy of the cured product (three-dimensional modeled product) by the powder material (layer) for modeled product is improved.
The average thickness may be determined by, for example, embedding the three-dimensional modeling powder material in an acrylic resin or the like and then performing etching or the like to expose the surface of the base material, followed by a scanning tunneling microscope STM, an atomic force microscope AFM. By using a scanning electron microscope SEM or the like, it can be measured.

There is no restriction | limiting in particular as the coverage (area ratio) of the surface of the said base material by the said organic material, Although it can select suitably according to the objective, 15% or more is preferable, 50% or more is more preferable, 80 % Or more is particularly preferable.
When the coverage is 15% or more, the strength of the cured product (three-dimensional model) by the three-dimensional model powder material (layer) formed by applying the composition liquid to the three-dimensional model powder material is sufficient. The obtained three-dimensional object powder material (layer) is formed without problems such as loss of shape during subsequent processing such as sintering or handling, and by applying the composition liquid to the three-dimensional object powder material. ) Improves the dimensional accuracy of the cured product (three-dimensional model).
The coverage is, for example, a portion of the three-dimensional modeling powder material observed in a three-dimensional modeling powder material and coated with the organic material with respect to the entire surface area of the particle in the two-dimensional modeling powder material. An average value of the area ratio (%) may be calculated, and this may be used as the coverage, or the portion covered with the organic material may be elementally mapped by energy dispersive X-ray spectroscopy such as SEM-EDS Can be measured.

-Other ingredients-
There is no restriction | limiting in particular as said other component, Although it can select suitably according to the objective, For example, a fluidizing agent, a filler, a leveling agent, a sintering aid, etc. are mentioned. When the powder material for three-dimensional modeling contains the fluidizing agent, it is preferable in that a layer of the powder material for three-dimensional modeling can be easily and efficiently formed, and a cured product (three-dimensional modeled product) obtained when the filler is included. ) Is preferable in that voids or the like are less likely to be generated, and when the leveling agent is included, the wettability of the three-dimensional modeling powder material is improved and handling is facilitated, and when the sintering aid is included, When the obtained cured product (three-dimensional modeled product) is subjected to a sintering treatment, it is preferable in that sintering at a lower temperature is possible.

-Manufacture of powder material for 3D modeling-
There is no restriction | limiting in particular as a manufacturing method of the said powder material for three-dimensional model | molding, According to the objective, it can select suitably, For example, the method etc. which coat | cover the said organic material on the said base material according to the well-known coating method etc. are suitable. It is mentioned in.
The method for coating the surface of the base material with the organic material is not particularly limited and can be appropriately selected from known coating methods. Examples of the coating method include rolling fluid coating method, Suitable examples include spray drying, stirring and mixing, dipping, and kneader coating. Moreover, these coating methods can be implemented using various well-known commercially available coating apparatuses, granulating apparatuses, and the like.

-Physical properties of powder materials for solid modeling-
There is no restriction | limiting in particular as an average particle diameter of the said powder material for three-dimensional modeling, Although it can select suitably according to the objective, 3 micrometers or more and 250 micrometers or less are preferable, 3 micrometers or more and 200 micrometers or less are more preferable, and 5 micrometers or more and 150 micrometers or less are preferable. More preferably, it is 10 μm or more and 85 μm or less.
When the average particle size is 3 μm or more, the fluidity of the powder material is improved, the powder material layer is easy to form, and the smoothness of the surface of the laminated layer is improved. However, the dimensional accuracy tends to improve. Further, when the average particle diameter is 250 μm or less, the size of the space between the powder material particles becomes small, so that the void ratio of the shaped article becomes small, which contributes to improvement in strength. Therefore, an average particle diameter of 3 μm or more and 250 μm or less is a preferable range for achieving both dimensional accuracy and strength.
There is no restriction | limiting in particular as a particle size distribution of the said powder material for three-dimensional model | molding, According to the objective, it can select suitably.

When the angle of repose is measured, the characteristic of the powder material for three-dimensional modeling is preferably 60 degrees or less, more preferably 50 degrees or less, and still more preferably 40 degrees or less.
When the angle of repose is 60 degrees or less, the powder material for three-dimensional modeling can be efficiently and stably disposed at a desired place on the support.
The angle of repose can be measured using, for example, a powder property measuring device (powder tester PT-N type, manufactured by Hosokawa Micron Corporation).

  The three-dimensional modeling powder material can be suitably used for simple and efficient manufacturing of various types of modeling objects. It can be particularly preferably used.

  A structure having a complicated three-dimensional shape can be easily and efficiently manufactured with high dimensional accuracy by simply applying the three-dimensional modeling composition liquid of the present invention to the three-dimensional modeling powder material of the present invention. The structure thus obtained is a cured product (three-dimensional model) having sufficient hardness, and can be held by hand, put in and out of the mold, or air blow processed to remove excess three-dimensional model powder material. Even if it does, shape loss does not occur, and it is excellent in handling property and handling property. The cured product may be used as it is, or may be further subjected to a sintering treatment as a cured product for sintering to form a sintered body of a three-dimensional model. In the case where the sintering treatment is performed, an unnecessary void or the like is not generated in the sintered body after sintering, and a sintered body having a beautiful appearance can be easily obtained.

<3D objects>
A structure having a complicated and high-strength three-dimensional shape can be easily and efficiently manufactured with high dimensional accuracy by allowing the three-dimensional modeling composition of the present invention to act on the three-dimensional modeling powder material and drying it as necessary. can do. The structure thus obtained is a cured product (three-dimensional model) having sufficient hardness, and can be held by hand, put in and out of the mold, or air blow processed to remove excess three-dimensional model powder material. Even if it is done, it does not lose its shape and is excellent in handling and handling. The cured product may be used as it is, or may be further subjected to a sintering treatment as a cured product for sintering to form a sintered body of a three-dimensional model. When the sintering process is performed, the sintered body after the sintering process is dense with few voids and a beautiful appearance can be easily obtained.

  The strength of the three-dimensional model is, for example, such that the shape is not lost even if the surface is rubbed, and an air blow process is performed from a distance of 5 cm using an air gun having a nozzle diameter of 2 mm and an air pressure of 0.3 MPa. Even so, cracks and the like do not occur.

(Method and apparatus for manufacturing a three-dimensional model)
The manufacturing method of the three-dimensional molded item of this invention contains a powder material supply process and a powder material hardening process, and also includes other processes, such as a sintering process, as needed.
A three-dimensional structure is manufactured by repeating the powder material supply step and the powder material curing step.
The three-dimensional model manufacturing apparatus of the present invention includes a powder material supply unit, a powder material curing unit, a powder material storage unit in which a powder material is stored, and a composition liquid storage unit in which a three-dimensional modeling composition liquid is stored. And, if necessary, other means such as a composition liquid supplying means and a sintering means.

-Powder material supply process and powder material supply means-
The said powder material supply process is a process of supplying the powder material for three-dimensional modeling containing an organic material and a base material.
The said powder material supply means is a means to supply the powder material for three-dimensional modeling containing an organic material and a base material.
The three-dimensional modeling powder material is preferably supplied onto a support.

--- Support--
The support is not particularly limited as long as the three-dimensional modeling powder material can be placed thereon, can be appropriately selected according to the purpose, and has a table having a mounting surface for the three-dimensional modeling powder material. Examples thereof include a base plate in the apparatus shown in FIG. 1 of Japanese Utility Model Publication No. 2000-328106.
The surface of the support, that is, the mounting surface on which the three-dimensional modeling powder is mounted may be, for example, a smooth surface, a rough surface, or a flat surface. Although it may be a curved surface, it is preferable that the affinity with the organic material is low when the organic material in the powder material for three-dimensional modeling is dissolved and crosslinked by the action of the crosslinking agent.
When the affinity between the placement surface and the dissolved and crosslinked organic material is lower than the affinity between the base material and the dissolved and crosslinked organic material, the obtained three-dimensional structure is placed. It is preferable in that it can be easily removed from the surface.

--Formation of powder material layer--
There is no restriction | limiting in particular as a method of arrange | positioning the said powder material for three-dimensional model | molding on the said support body, Although it can select suitably according to the objective, For example, as a method of arrange | positioning in a thin layer, patent 3607300 A method using a known counter rotation mechanism (counter roller) used in the selective laser sintering method described in the publication, and the three-dimensional modeling powder material is spread into a thin layer using a member such as a brush, a roller, or a blade. Preferred examples include a method, a method of pressing the surface of the three-dimensional modeling powder using a pressing member to expand the powder into a thin layer, a method using a known powder laminating apparatus, and the like.

In order to place the powder material for three-dimensional modeling in a thin layer on the support using the counter rotating mechanism (counter roller), the brush or blade, the pressing member, etc., for example, as follows: It can be carried out.
That is, the support disposed in the outer frame (sometimes referred to as “mold”, “hollow cylinder”, “tubular structure”, etc.) so as to be movable up and down while sliding on the inner wall of the outer frame. The three-dimensional modeling powder material is placed on the body using the counter rotation mechanism (counter roller), the brush, a roller or a blade, the pressing member, and the like. At this time, when using the support that can move up and down in the outer frame, the support is arranged at a position slightly lower than the upper end opening of the outer frame, that is, the three-dimensional modeling The three-dimensional modeling powder material is placed on the support by being positioned below the thickness of the powder material layer for use. By the above, the said three-dimensional modeling powder material can be mounted in a thin layer on the said support body.

In addition, when the said composition liquid for three-dimensional modeling is made to act on the said powder material for three-dimensional modeling placed in the thin layer in this way, the said layer will harden | cure.
The three-dimensional modeling powder material (layer) placed on the thin layer is placed on the thin layer of the cured product obtained in the same manner as described above. On the other hand, when the said composition liquid is made to act, hardening will arise. The hardening at this time is not only in the powder material (layer) for three-dimensional modeling placed on the thin layer, but also with the hardened product of the thin layer obtained by hardening first, which exists under the material. It also occurs between. As a result, a cured product (three-dimensional model) having a thickness of about two layers of the three-dimensional model powder material (layer) placed on the thin layer is obtained.

  Moreover, in order to mount the said powder material for three-dimensional modeling in a thin layer on the said support body, it can also carry out automatically and simply using the said well-known powder lamination apparatus. The powder laminating apparatus generally includes a recoater for laminating the three-dimensional modeling powder material, a movable supply tank for supplying the three-dimensional modeling powder material onto the support, and the three-dimensional modeling powder material. Is mounted on a thin layer and includes a movable molding tank for stacking. In the powder laminating apparatus, the surface of the supply tank can always be slightly raised from the surface of the molding tank by raising the supply tank, lowering the molding tank, or both. The powder material for three-dimensional modeling can be arranged in a thin layer using the recoater from the supply tank side, and the powder material for three-dimensional modeling can be laminated by repeatedly moving the recoater. .

The thickness of the powder material layer for three-dimensional modeling is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the average thickness per layer is preferably 30 μm or more and 500 μm or less, and 60 μm or more and 300 μm or less. More preferred.
When the thickness is 30 μm or more, the strength of the cured product (three-dimensional model) by the three-dimensional model powder material (layer) formed by applying the composition liquid to the three-dimensional model powder material is sufficient, A powder material for a three-dimensional structure formed by applying the composition liquid to the powder material for three-dimensional structure (500 μm or less) such that a problem such as loss of shape does not occur during subsequent processing such as sintering or handling. The dimensional accuracy of the cured product (three-dimensional model) by the layer is improved.
The average thickness is not particularly limited and can be measured according to a known method.

-Powder material curing process and powder material curing means-
The powder material curing step is a step in which the three-dimensional modeling composition liquid is applied to the three-dimensional modeling powder material supplied in the powder material supplying step to cure a predetermined region of the powder material.
The powder material curing unit is a unit that applies the three-dimensional modeling composition liquid to the three-dimensional modeling powder material supplied by the powder material supply unit and cures a predetermined region of the powder material.

The method for applying the three-dimensional modeling composition liquid to the powder material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a dispenser method, a spray method, and an ink jet method. In order to carry out these methods, a known apparatus can be suitably used as the composition liquid applying means.
Among these, the dispenser method is excellent in droplet quantification, but the application area is narrow, and the spray method can easily form a fine discharge, the application area is wide, and the application property is excellent. The quantitative property of the droplets is poor, and powder scattering occurs due to the spray flow. For this reason, in the present invention, the ink jet method is particularly preferable. Compared to the spray method, the ink jet method has an advantage that the quantitative property of the droplet is better, and compared with the dispenser method, there is an advantage that the application area can be widened, and a complicated three-dimensional shape can be formed accurately and efficiently. preferable.

  When the ink jet method is used, the powder material curing means has a nozzle capable of applying the three-dimensional modeling composition liquid to the powder material by the ink jet method. In addition, as the nozzle, a nozzle (discharge head) in a known ink jet printer can be suitably used, and the ink jet printer can be suitably used as the powder material curing means. In addition, as said inkjet printer, SG7100 by Ricoh Co., Ltd. etc. are mentioned suitably, for example. The ink jet printer is preferable in that the amount of the composition liquid that can be dropped from the head portion at a time is large and the application area is large, so that the application speed can be increased.

  In the present invention, even when the inkjet printer capable of applying the three-dimensional modeling composition liquid of the present invention with high accuracy and high efficiency is used, the composition liquid is a solid material such as particles or a resin or the like. Since no high-viscosity molecular material is contained, clogging or the like does not occur in the nozzle or its head, corrosion does not occur, and when applied (discharged) to the three-dimensional modeling powder material layer , Because it is possible to efficiently penetrate into the organic material in the powder material for three-dimensional modeling, it is excellent in manufacturing efficiency of a three-dimensional modeled object, and a polymer component such as a resin is not added, so an unexpected increase in volume This is advantageous in that a cross-linked product with good dimensional accuracy can be obtained easily and efficiently in a short time.

-Powder material container-
The powder material container is a member in which the three-dimensional modeling powder material is stored, and the size, shape, material, and the like thereof are not particularly limited and can be appropriately selected according to the purpose. A tank, a bag, a cartridge, a tank, etc. are mentioned.

-Composition liquid container-
The composition liquid storage unit is a member in which the three-dimensional modeling composition liquid is stored, and the size, shape, material, and the like thereof are not particularly limited and can be appropriately selected according to the purpose. A tank, a bag, a cartridge, a tank, etc. are mentioned.

-Other processes and other means-
Examples of the other steps include a drying step, a sintering step, a surface protection treatment step, and a painting step.
Examples of the other means include drying means, sintering means, surface protection treatment means, and painting means.

  The said drying process is a process of drying the hardened | cured material (three-dimensional molded item) obtained in the said powder material hardening process. In the drying step, not only moisture contained in the cured product but also organic matter may be removed (degreasing). Examples of the drying means include known dryers.

  The said sintering process is a process of sintering the hardened | cured material (three-dimensional molded item) formed in the said powder material hardening process. By performing the sintering step, the cured product can be made into a sintered body of an integrated metal or ceramic three-dimensional structure. Examples of the sintering means include a known sintering furnace.

The said surface protection treatment process is a process of forming a protective layer etc. on the hardened | cured material (three-dimensional molded item) formed in the said powder material hardening process. By performing this surface protection treatment step, it is possible to provide the surface of the cured product (three-dimensional model) with durability that allows the cured product (three-dimensional model) to be used as it is, for example. Specific examples of the protective layer include a water resistant layer, a weather resistant layer, a light resistant layer, a heat insulating layer, and a glossy layer. Examples of the surface protection treatment means include known surface protection treatment devices such as a spray device and a coating device.
The coating process is a process of coating the cured product (three-dimensional model) formed in the powder material layer curing process. By performing the coating step, the cured product (three-dimensional model) can be colored in a desired color. Examples of the coating means include known coating apparatuses, such as a coating apparatus using a spray, a roller, a brush, and the like.

Here, FIG. 1 shows an example of the powder additive manufacturing apparatus of the present invention. 1 has a modeling-side powder storage tank 1 and a supply-side powder storage tank 2, and each of these powder storage tanks has a stage 3 that can move up and down. A powder material for a three-dimensional structure is stored in
On the modeling side powder storage tank 1, it has the inkjet head 5 which discharges the three-dimensional modeling composition liquid 4 toward the powder material for modeling objects in this powder storage tank, and also from the supply side powder storage tank 2 A leveling mechanism 6 (hereinafter sometimes referred to as a recoater) that supplies powder material for a three-dimensional structure to the modeling-side powder storage tank 1 and also smoothes the surface of the powder material for a three-dimensional structure in the modeling-side powder storage tank 1. Have.

A three-dimensional composition liquid is dropped from the inkjet head 5 onto the three-dimensionally shaped powder material in the modeling-side powder storage tank 1. At this time, the position where the three-dimensional modeling composition liquid is dropped is determined by two-dimensional image data (slice data) obtained by slicing a three-dimensional shape to be finally modeled into a plurality of plane layers.
After the drawing for one layer is completed, the stage 3 of the supply-side powder storage tank 2 is raised, and the stage 3 of the modeling-side powder storage tank 1 is lowered. The powder material for the three-dimensional modeled object of the difference is moved to the modeling side powder storage tank 1 by the leveling mechanism 6.

In this way, a new powder layer for a three-dimensional object is formed on the previously drawn powder surface for a three-dimensional object. At this time, the thickness of one layer of the molded article powder layer is about several tens of μm to 100 μm.
By performing drawing based on the slice data of the second layer on the newly formed powder layer for a three-dimensional structure, repeating this series of processes to obtain a structure, and heating and drying with a heating means (not shown) A model is obtained.

FIG. 2 shows another example of the powder additive manufacturing apparatus of the present invention. The powder additive manufacturing apparatus in FIG. 2 is the same as that in FIG. 1 in principle, but the supply mechanism of the powder material for a three-dimensional object is different. That is, the supply side powder storage tank 2 is arranged above the modeling side powder storage tank 1. When the drawing of the first layer is completed, the stage 3 of the modeling-side powder storage tank 1 is lowered by a predetermined amount, and the supply-side powder storage tank 2 is moved while a predetermined amount of the powder material for modeling objects is transferred to the modeling-side powder storage tank 1. It is dropped and a new powder material layer for a model is formed. After that, the leveling mechanism 6 compresses the molded material powder material to increase the bulk density and uniformly level the height of the molded material powder material.
According to the powder additive manufacturing apparatus having the configuration shown in FIG. 2, the apparatus can be made compact compared to the configuration of FIG. 1 in which two powder storage tanks are arranged in a plane.

By using the manufacturing method and manufacturing apparatus for a three-dimensional object according to the present invention described above, a three-dimensional object having a complicated three-dimensional shape (three-dimensional (3D)) is used for the three-dimensional object composition according to the present invention or the three-dimensional object material set. And can be manufactured with good dimensional accuracy without causing deformation before sintering or the like.
The three-dimensional model obtained in this way has sufficient strength, excellent dimensional accuracy, a dense sintered body with few voids, and can reproduce fine irregularities, curved surfaces, etc., so it has excellent aesthetic appearance, It is of high quality and can be suitably used for various applications.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Production example 1 of powder material for three-dimensional modeling)
-Preparation of coating solution 1-
114 parts by mass of water was mixed with 6 parts by mass of acetoacetyl group-modified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Co., Ltd., Gohsenx Z-100, average polymerization degree: 500, saponification degree 98.5 mol%) which is a water-soluble resin. Next, while heating at 90 ° C. in a water bath, the mixture was stirred for 1 hour using a three-one motor (manufactured by Shinto Kagaku Co., Ltd., BL600) to dissolve the acetoacetyl group-modified polyvinyl alcohol in the water. In this way, 120 mass parts of 5 mass% acetoacetyl group modified polyvinyl alcohol aqueous solution was prepared. The obtained preparation liquid was designated as coating liquid 1.
The viscosity at 20 ° C. of a 4% by mass (w / w%) aqueous solution of the acetoacetyl group-modified polyvinyl alcohol was measured with a viscometer (Brookfield Rotational Viscometer, DV-E VISCOMETER HADVE115 type). 5.0 mPa · s to 6.0 mPa · s.

-Coating of the coating liquid 1 on the substrate surface-
Next, using a commercially available coating device (MP-01, manufactured by Paulec), 100 parts by mass of stainless steel (SUS316L) powder (manufactured by Sanyo Special Steel Co., Ltd., PSS316L, volume average particle size 41 μm) as the base material. On the other hand, the coating solution 1 was coated so that the coating thickness (average thickness) was 100 nm. In this coating, sampling was performed as needed, and the coating time and interval were appropriately adjusted so that the coating thickness (average thickness) of the coating liquid 1 was 100 nm and the coverage (%) was 100%. Thus, the powder material 1 for three-dimensional modeling was obtained. In addition, the measuring method of coating thickness and surface coverage, and the conditions of the said coating were shown below.

<Coating thickness (average thickness)
The coating thickness (average thickness) was obtained by polishing the surface of the three-dimensional modeling powder material 1 with emery paper, and then lightly polishing the surface with a cloth soaked in water to dissolve the resin site, thereby preparing an observation sample. . Next, the boundary portion between the base material portion and the resin portion exposed on the surface is observed with a field emission scanning electron microscope (FE-SEM), and the length between the resin portion surface and the boundary portion is defined as the coating thickness. It was measured. The average value of 10 measurement locations was determined and this was taken as the coating thickness (average thickness).

<Surface coverage>
Using a field emission scanning electron microscope (FE-SEM), a backscattered electron image (ESB) was photographed under the following conditions with a field setting in which about 10 of the three-dimensional modeling powder material 1 was within the screen, and ImageJ software was used. Binarization was performed by image processing. The black part was the covering part and the white part was the base part, and the ratio was determined by the black part area in one particle / (black part area + white part area) × 100. Ten particles were measured, and the average value was defined as the surface coverage (%).
-SEM observation conditions-
Signal: ESB (reflection electron image)
・ EHT: 0.80kV
・ ESB Grid: 700V
・ WD: 3.0mm
・ Aperture Size: 30.00μm
・ Contrast: 80%
-Magnification: Set for each sample to fit about 10 in the horizontal direction of the screen

<Coating conditions>
・ Spray setting Nozzle type 970
Nozzle diameter 1.2mm
Coating liquid discharge pressure 4.7 Pa · s
Coating liquid discharge speed 3g / min
Atomized air volume 50 NL / min
・ Rotor setting Rotor model M-1
Rotation speed 60rpm
Rotation speed 400%
・ Airflow setting Supply air temperature 80 ℃
Supply air volume 0.8m ³ / min
Bag filter discharge pressure 0.2 MPa
Bag filter dropout time 0.3 seconds Bug filter interval 5 seconds ・ Coating time 40 minutes

  It was 43 micrometers when the average particle diameter was measured about the obtained powder material 1 for three-dimensional modeling using the commercially available particle size measuring apparatus (The Nikkiso Co., Ltd. make, Microtrac HRA). Further, the repose angle as a fluidity was measured using a commercially available repose angle measuring device (Phospo Tester PT-N type, manufactured by Hosokawa Micron Corporation), and found to be 35 degrees. In addition, it exists in the tendency for fluidity | liquidity to become worse, so that the measured value of this angle of repose is large.

-Preparation of composition liquid 1 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 1 Rare Element Chemical Industries, Ltd., Zircosol AC-20) 3 parts by mass and 2-amino-2-ethyl-1,3-propanediol (AEPD, Tokyo Chemical Industry Co., Ltd.) as a stabilizer 0. 3 parts by mass and 0.1 part by mass of polyvinylpyrrolidone K-90 (BASF Corporation, weight average molecular weight 1,400,000) as a water-soluble resin are dispersed for 30 minutes using a homomixer, A composition liquid 1 was prepared.

  About the obtained composition liquid 1 for three-dimensional modeling, storage stability was evaluated as follows. The results are shown in Table 1.

<Storage stability>
The three-dimensional modeling composition liquid 1 was put in a polypropylene wide-mouth bottle (capacity: 50 mL), left in a thermostatic bath at 50 ° C. for 30 days, and then taken out from the thermostatic bath. The composition solution 1 for three-dimensional modeling taken out from the thermostat was allowed to stand until it reached room temperature (25 ° C.), and then the viscosity was measured. The viscosity of the three-dimensional modeling composition liquid 1 before being put into the thermostat was set as the viscosity before storage, and the viscosity of the three-dimensional modeling composition liquid after being taken out from the thermostat was set as the viscosity after storage, and the viscosity change rate was calculated by the following formula. The viscosity before storage and the viscosity after storage were measured at 25 ° C. using an R-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
Viscosity change rate (%) = [(viscosity after storage) − (viscosity before storage)] / (viscosity before storage) × 100
[Evaluation criteria]
× ・ ・ ・ Viscosity change rate is 20% or more △ ・ ・ ・ Viscosity change rate is 10% or more and less than 20% ○ ・ ・ ・ Viscosity change rate is 5% or more and less than 10% ◎ ・ ・ ・ Viscosity change rate is less than 5%

Example 1
The obtained three-dimensional modeling powder material 1 and the three-dimensional modeling composition liquid 1 are manufactured as follows using a shape printing pattern of size (length 70 mm × width 12 mm). did. In addition, the said composition liquid 1 for three-dimensional model | molding used what was left to stand until it became room temperature, after leaving to stand in a 50 degreeC thermostat for 30 days.
(1) First, using the manufacturing apparatus for a three-dimensional structure as shown in FIG. 1, the three-dimensional structure powder material 1 is transferred from the supply-side powder storage tank to the supply-side powder storage tank, and then on the support. The powder material 1 for three-dimensional modeling was supplied so that the average thickness was 100 μm.
(2) Next, the three-dimensional modeling composition liquid 1 was applied (discharged) to the surface of the supplied three-dimensional modeling powder material 1 from a nozzle of a known inkjet discharge head. The polyvinyl alcohol was dissolved in water contained in the curing liquid 1, and the acetoacetyl group-modified polyvinyl alcohol was crosslinked by the action of a crosslinking agent (zirconium carbonate ammonium salt) contained in the three-dimensional modeling composition liquid 1.

(3) Next, the operations of (1) and (2) are repeated until a total average thickness of 3 mm is reached, and a thin layer of the solid three-dimensional modeling powder material 1 is sequentially laminated and dried. Using a machine, it was maintained at 65 ° C. for 4 hours and then at 140 ° C. for 10 hours, and a drying process was performed to obtain a three-dimensional structure 1.

When the three-dimensional structure 1 after drying, the excess powder material 1 for three-dimensional structure was removed by air blowing, the shape was not lost, and the strength and dimensional accuracy were excellent.
The strength (hardness) and dimensional accuracy were evaluated according to the following criteria. The results are shown in Table 1.

<Strength (hardness)>
X: The three-dimensional modeling powder material is not sufficiently cured, and the three-dimensional modeling material cannot be taken out from the laminated three-dimensional modeling powder material, and when it is taken out, the predetermined shape cannot be maintained. ... It is possible to take out a three-dimensional object from the laminated three-dimensional powder material, and it is possible to take out unnecessary three-dimensional powder material by adjusting the air blow pressure or using a brush. There is a state in which the three-dimensional model can maintain its shape. Even if a strong air blow is performed on the three-dimensional model, only the unnecessary three-dimensional model powder material is removed, and the three-dimensional model itself has its shape. Maintained state ◎ ・ ・ ・ Three-dimensional model is fully cured and not easily broken

<Dimensional accuracy>
X: Distortion has occurred on the surface of the three-dimensional structure, and when the surface is observed, uneven distribution of the base material and the organic material is observed. Δ: Some distortion and unevenness on the surface of the three-dimensional structure. The surface state of the three-dimensional structure is good, but the surface is slightly warped. The surface of the three-dimensional structure is smooth and beautiful, and there is no warping. State

(4) For the three-dimensional structure 1 obtained in (3) above, using a dryer, the temperature is increased to 400 ° C. in a nitrogen atmosphere to perform a degreasing step, and further, in a sintering furnace under vacuum conditions, Sintering was performed at 1,300 ° C. As a result, a three-dimensional structure 1 (sintered body) having a beautiful surface was obtained.
This three-dimensional structure 1 is a completely integrated stainless steel structure (metal lump), and no damage or the like occurred even when it was hit against a hard floor.

(Example 2)
In Example 1, the three-dimensional structure 2 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 2 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 1.

-Preparation of composition liquid 2 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 3 parts by mass of Zircosol AC-20) manufactured by One Rare Element Chemical Co., Ltd., 0.3 parts by mass of dihydroxyethylglycine salt (Cyrest G-50, manufactured by Crest Co., Ltd.) as a stabilizer, and water-soluble resin 3 parts of polyvinylpyrrolidone K-90 (manufactured by BASF, weight average molecular weight 1,400,000) was dispersed for 30 minutes using a homomixer to prepare a three-dimensional composition solution 2. About the obtained composition liquid 2 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 1.

(Example 3)
In Example 1, the three-dimensional structure 3 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 3 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 1.

-Preparation of three-dimensional modeling composition 3-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 3 parts by mass of Zircosol AC-20) manufactured by One Rare Element Chemical Co., Ltd., 0.3 parts by mass of dihydroxyethylglycine salt (Cyrest G-50, manufactured by Crest Co., Ltd.) as a stabilizer, and water-soluble resin 1 part by weight of polyvinylpyrrolidone K-90 (manufactured by BASF, weight average molecular weight 1,400,000) was dispersed for 30 minutes using a homomixer to prepare a composition solution 3 for three-dimensional modeling. About the obtained composition liquid 3 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 1.

Example 4
In Example 1, the three-dimensional structure 4 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 4 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 2.

-Preparation of composition liquid 4 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 1 Rare Element Chemical Industries, Ltd., Zircosol AC-20) 3 parts by mass and 2-amino-2-ethyl-1,3-propanediol (AEPD, Tokyo Chemical Industry Co., Ltd.) as a stabilizer 0. 3 parts by mass and 0.5 part by mass of polyvinylpyrrolidone K-85 (manufactured by Nippon Shokubai Co., Ltd., weight average molecular weight 1,000,000) as a water-soluble resin were dispersed using a homomixer for 30 minutes, A three-dimensional modeling composition liquid 4 was prepared. About the obtained composition liquid 4 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 2.

(Example 5)
In Example 1, the three-dimensional model 5 was manufactured in the same manner as in Example 1 except that the three-dimensional model composition liquid 1 was replaced with the three-dimensional model composition liquid 5 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 2.

-Preparation of composition liquid 5 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 3 parts by mass of Zircozol AC-20), manufactured by One Rare Element Chemical Co., Ltd., 0.3 parts by mass of phosphonobutanetricarboxylate (Cyrest PH-435, manufactured by Crest Co., Ltd.) as a stabilizer, and water-soluble 3 parts by mass of a 35 mass% aqueous solution of polyvinyl pyrrolidone K-60 as a resin (manufactured by Tokyo Chemical Industry Co., Ltd., weight average molecular weight 450,000) is dispersed for 30 minutes using a homomixer, and the composition liquid for three-dimensional modeling 5 was prepared. About the obtained composition liquid 5 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 2.

(Example 6)
In Example 1, the three-dimensional structure 6 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 6 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 2.

-Preparation of composition liquid 6 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 1 Rare Element Chemical Industries, Ltd., Zircosol AC-20) 3 parts by mass and 2-amino-2-ethyl-1,3-propanediol (AEPD, Tokyo Chemical Industry Co., Ltd.) as a stabilizer 0. 3 parts by mass and 0.1 part by mass of polyvinylpyrrolidone K-30 (Daiichi Kogyo Seiyaku Co., Ltd., weight average molecular weight 50,000) as a water-soluble resin were dispersed for 30 minutes using a homomixer, A three-dimensional modeling composition 6 was prepared. About the obtained composition liquid 6 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 2.

(Example 7)
In Example 1, the three-dimensional structure 7 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 7 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 3.

-Preparation of composition liquid 7 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 3 parts by mass of Zircosol AC-20) manufactured by One Rare Element Chemical Co., Ltd., 0.3 parts by mass of dihydroxyethylglycine salt (Cyrest G-50, manufactured by Crest Co., Ltd.) as a stabilizer, and water-soluble resin Of polyvinyl pyrrolidone K-30 (Daiichi Kogyo Seiyaku Co., Ltd., weight average molecular weight 50,000) was dispersed for 30 minutes using a homomixer to prepare a three-dimensional modeling composition liquid 7. . About the obtained three-dimensional modeling composition liquid 7, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 3.

(Example 8)
In Example 1, the three-dimensional structure 8 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 8 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 3.

-Preparation of composition liquid 8 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 3 parts by mass of Zircozol AC-20), manufactured by One Rare Element Chemical Co., Ltd., 0.3 parts by mass of phosphonobutanetricarboxylate (Cyrest PH-435, manufactured by Crest Co., Ltd.) as a stabilizer, and water-soluble One part by weight of polyvinyl pyrrolidone K-30 (made by Daiichi Kogyo Seiyaku Co., Ltd., weight average molecular weight 50,000) as a resin was dispersed for 30 minutes using a homomixer to prepare a composition solution 8 for three-dimensional modeling. . About the obtained composition liquid 8 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 3.

Example 9
In Example 1, the three-dimensional model 9 was manufactured and carried out in the same manner as in Example 1 except that the three-dimensional model composition liquid 1 was replaced with the three-dimensional model composition liquid 9 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 3.

-Preparation of composition liquid 9 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 3 parts by mass of Zircozol AC-20), manufactured by One Rare Element Chemical Co., Ltd., 0.3 parts by mass of phosphonobutanetricarboxylate (Cyrest PH-435, manufactured by Crest Co., Ltd.) as a stabilizer, and water-soluble 3 parts by mass of polyvinyl pyrrolidone K-30 (made by Daiichi Kogyo Seiyaku Co., Ltd., weight average molecular weight 50,000) as a resin was dispersed for 30 minutes using a homomixer to prepare a composition solution 8 for three-dimensional modeling. . About the obtained composition liquid 8 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 3.

(Example 10)
In Example 1, the three-dimensional structure 10 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 10 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 4.

-Preparation of 3D modeling composition 10-
70 parts by mass of water as a solvent, 30 parts by mass of 3-methyl-1,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. is 15.05 mmHg) as a water-soluble organic solvent, and a crosslinking agent 3 parts by mass of zirconium ammonium carbonate (Zircozol AC-20, manufactured by Daiichi Rare Element Chemical Co., Ltd.) and 2-amino-2-ethyl-1,3-propanediol (AEPD, Tokyo) as a stabilizer 0.3 parts by mass (made by Kasei Kogyo Co., Ltd.) and 0.1 parts by mass of polyvinylpyrrolidone K-90 (BASF, weight average molecular weight 1,400,000) as a water-soluble resin, using a homomixer The composition liquid 10 for three-dimensional modeling was prepared by dispersing for 30 minutes. About the obtained composition liquid 10 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 4.

(Example 11)
In Example 1, the three-dimensional structure 11 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 11 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 4.

-Preparation of composition liquid 11 for three-dimensional modeling-
70 parts by mass of water as a solvent, 30 parts by mass of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium lactate ammonium salt (Orga as a crosslinking agent) Chicks ZC-300, manufactured by Matsumoto Fine Chemical Co., Ltd.) 3 parts by mass, and 2-amino-2-ethyl-1,3-propanediol (AEPD, manufactured by Tokyo Chemical Industry Co., Ltd.) as a stabilizer, 0.3 parts by mass And 1 part by mass of polyvinylpyrrolidone K-90 (BASF, weight average molecular weight 1,400,000) as a water-soluble resin are dispersed for 30 minutes using a homomixer, and the three-dimensional modeling composition liquid 11 is obtained. Prepared.
About the obtained composition liquid 11 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 4.

(Example 12)
In Example 1, the three-dimensional model 12 was manufactured and carried out in the same manner as in Example 1 except that the three-dimensional model composition liquid 1 was replaced with the three-dimensional model composition liquid 12 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 4.

-Preparation of composition liquid 12 for three-dimensional modeling-
70 parts by mass of water as a solvent, 30 parts by mass of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium lactate ammonium salt (Orga as a crosslinking agent) Chicks ZC-300 (manufactured by Matsumoto Fine Chemical Co., Ltd.) 3 parts by mass, dihydroxyethyl glycine salt as a stabilizer (Cyrest Co., Ltd., Kirest G-50) 0.3 part by mass, and polyvinylpyrrolidone as a water-soluble resin One-part K-85 (manufactured by Nippon Shokubai Co., Ltd., weight average molecular weight 1,000,000) was dispersed for 30 minutes using a homomixer to prepare a three-dimensional modeling composition liquid 12.
About the obtained composition liquid 12 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 4.

(Example 13)
In Example 1, the three-dimensional structure 13 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 13 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 5.

-Preparation of composition liquid 13 for three-dimensional modeling-
70 parts by mass of water as a solvent, 30 parts by mass of 3-methyl-1,3-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. is 15.05 mmHg) as a water-soluble organic solvent, and a crosslinking agent 3 parts by mass of zirconium ammonium carbonate (Zircozol AC-20, manufactured by Daiichi Rare Element Chemical Co., Ltd.) and 0.3 mg of dihydroxyethylglycine salt (Cylest G-50, manufactured by Kirest Co., Ltd.) as a stabilizer Disperse 30 parts by weight using a homomixer with 5 parts by weight of a 35 part by weight aqueous solution of polyvinyl pyrrolidone K-60 (manufactured by Tokyo Chemical Industry Co., Ltd., weight average molecular weight 450,000) as a water-soluble resin. The composition liquid 13 for three-dimensional modeling was prepared.
About the obtained three-dimensional model | molding composition liquid 13, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 5.

(Example 14)
In Example 1, the three-dimensional structure 14 was manufactured in the same manner as in Example 1, except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 14 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 5.

-Preparation of composition liquid 14 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 1 Rare Element Chemical Industries, Ltd., Zircosol AC-20) 3 parts by mass and 2-amino-2-ethyl-1,3-propanediol (AEPD, Tokyo Chemical Industry Co., Ltd.) as a stabilizer 0. 3 parts by mass and 0.1 part by mass of polyethylene glycol (“PEG 500,000”, manufactured by Wako Pure Chemical Industries, Ltd., first grade, weight average molecular weight Mw = 500,000) as a water-soluble resin, The composition liquid 14 for three-dimensional modeling was prepared by dispersing for 30 minutes.
About the obtained three-dimensional modeling composition liquid 14, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 5.

(Example 15)
In Example 1, the three-dimensional structure 15 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 15 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 5.

-Preparation of composition liquid 15 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 1 Rare Element Chemical Industries, Ltd., Zircosol AC-20) 3 parts by mass and 2-amino-2-ethyl-1,3-propanediol (AEPD, Tokyo Chemical Industry Co., Ltd.) as a stabilizer 0. 3 parts by mass and 0.5 part by mass of polyethylene glycol (“PEG 500,000”, manufactured by Wako Pure Chemical Industries, Ltd., first grade, weight average molecular weight Mw = 500,000) as a water-soluble resin, It was used and dispersed for 30 minutes to prepare a three-dimensional modeling composition liquid 15.
About the obtained three-dimensional modeling composition liquid 15, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in 5.

(Comparative Example 1)
In Example 1, the three-dimensional structure 16 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 16 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 6.

-Preparation of composition liquid 16 for three-dimensional modeling-
70 parts by mass of water as a solvent, 30 parts by mass of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium lactate ammonium salt (Orga as a crosslinking agent) Chicks ZC-300, manufactured by Matsumoto Fine Chemical Co., Ltd.) 3 parts by mass, and 2-amino-2-ethyl-1,3-propanediol (AEPD, manufactured by Tokyo Chemical Industry Co., Ltd.) as a stabilizer, 0.3 parts by mass And 15 parts by mass of polyvinylpyrrolidone K-15 (manufactured by Tokyo Chemical Industry Co., Ltd., weight average molecular weight 10,000) as a water-soluble resin are dispersed for 30 minutes using a homomixer, and the three-dimensional modeling composition liquid 16 Was prepared. About the obtained composition liquid 16 for three-dimensional modeling, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 6.

(Comparative Example 2)
In Example 1, the three-dimensional structure 17 was manufactured in the same manner as in Example 1 except that the three-dimensional composition liquid 1 was replaced with the three-dimensional composition liquid 17 prepared as follows. Evaluation similar to Example 1 was performed. The results are shown in Table 6.

-Preparation of composition liquid 17 for three-dimensional modeling-
70 parts by weight of water as a solvent, 30 parts by weight of propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., vapor pressure at 100 ° C. of 20.19 mmHg) as a water-soluble organic solvent, and zirconium carbonate ammonium salt (No. 1) 3 parts by mass of Zircosol AC-20) manufactured by One Rare Element Chemical Co., Ltd., 0.3 parts by mass of dihydroxyethylglycine salt (Cyrest G-50, manufactured by Crest Co., Ltd.) as a stabilizer, and water-soluble resin 15 parts by mass of polyvinylpyrrolidone K-15 (manufactured by Tokyo Chemical Industry Co., Ltd., weight average molecular weight 10,000) was dispersed for 30 minutes using a homomixer to prepare a composition solution 17 for three-dimensional modeling. About the obtained three-dimensional model | molding composition liquid 17, it carried out similarly to Example 1, and evaluated storage stability. The results are shown in Table 6.

* "-" In Table 6 means that measurement is impossible.

Details of the abbreviations in Tables 1 to 6 are as follows.
* “AEPD”: 2-amino-2-ethyl-1,3-propanediol (manufactured by Tokyo Chemical Industry Co., Ltd.)
* "G-50": dihydroxyethyl glycine salt (manufactured by Kirest Co., Ltd., Kirest G-50)
* “PH-435”: Phosphonobutane tricarboxylate (manufactured by Kyrest Co., Ltd., Kyrest PH-435)
* “PEG 500,000”: polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., first grade, weight average molecular weight Mw = 500,000)

Aspects of the present invention are as follows, for example.
<1> A composition liquid for three-dimensional modeling used to form a three-dimensional modeled object composed of a three-dimensional model powder material including an organic material and a base material,
It is a composition liquid for three-dimensional modeling characterized by including the crosslinking agent which bridge | crosslinks with the said organic material, and the water-soluble resin whose weight average molecular weight is 50,000 or more.
<2> The three-dimensional modeling composition liquid according to <1>, wherein the water-soluble resin has a weight average molecular weight of 700,000 or more.
<3> The three-dimensional modeling composition liquid according to any one of <1> to <2>, wherein the water-soluble resin is polyvinylpyrrolidone.
<4> The three-dimensional modeling composition liquid according to any one of <1> to <3>, wherein the crosslinking agent is a metal salt.
<5> The three-dimensional modeling composition liquid according to any one of <1> to <4>, wherein the crosslinking agent is a zirconium compound.
<6> The composition liquid for three-dimensional modeling according to any one of <1> to <5>, further including at least one selected from an amino group-containing compound, a phosphono group-containing compound, and gluconic acid and a salt thereof. is there.
<7> The three-dimensional modeling composition liquid according to <6>, wherein the amino group-containing compound is any one of an amino group-containing polyhydric alcohol, a hydroxyl group-containing amine compound, and an amino group-containing chelating agent.
<8> The composition solution for three-dimensional modeling according to any one of <1> to <7>, including the solvent, wherein the solvent contains a water-soluble organic solvent having a vapor pressure of 10 mmHg or higher at 100 ° C.
<9> The composition solution for three-dimensional modeling according to any one of <1> to <8>, wherein the organic material can be dissolved.
<10> A three-dimensional modeling material set comprising: a three-dimensional modeling powder material including an organic material and a base material; and the three-dimensional modeling composition liquid according to any one of <1> to <9>. is there.
<11> The three-dimensional modeling material set according to <10>, wherein the base material is coated with the organic material.
<12> The three-dimensional modeling material set according to any one of <10> to <11>, wherein the base material is a base material that does not react with the three-dimensional modeling composition liquid.
<13> The three-dimensional modeling material set according to any one of <10> to <12>, wherein the base material is at least one of a metal and a ceramic.
<14> The three-dimensional modeling material set according to any one of <10> to <13>, wherein the organic material includes a water-soluble resin.
<15> The three-dimensional modeling material set according to <14>, wherein the water-soluble resin includes a modified polyvinyl alcohol resin.
<16> a powder material supply step for supplying a powder material for three-dimensional modeling including an organic material and a base material;
A powder material curing step of applying a three-dimensional modeling composition liquid to the supplied powder material and curing a predetermined region of the powder material;
Is a manufacturing method for manufacturing a three-dimensional modeled object,
3. The method for producing a three-dimensional structure, wherein the three-dimensional structure forming liquid is the three-dimensional structure forming liquid according to any one of <1> to <9>.
<17> The method for producing a three-dimensional structure according to <16>, further including a sintering step of sintering a three-dimensional structure manufactured by repeating the powder material supply step and the powder material curing step.
<18> Powder material supply means for supplying a powder material for three-dimensional modeling including an organic material and a base material;
Powder material curing means for applying the three-dimensional modeling composition liquid according to any one of <1> to <9> to the supplied powder material and curing a predetermined region of the powder material;
A powder material container in which the powder material for three-dimensional modeling is stored;
A curable liquid storage part in which the three-dimensional modeling composition liquid is stored;
It is the manufacturing apparatus of the three-dimensional molded item characterized by having.

DESCRIPTION OF SYMBOLS 1 Modeling side powder storage tank 2 Supply side powder storage tank 3 Stage 4 Composition liquid for three-dimensional modeling 5 Inkjet head 6 Leveling mechanism

JP 2004-330743 A JP 2005-297325 A

Claims (18)

It is a composition liquid for three-dimensional modeling used to form a three-dimensional model formed of a powder material for three-dimensional modeling including an organic material and a base material,
A composition solution for three-dimensional modeling, comprising: a crosslinking agent that crosslinks the organic material; and a water-soluble resin having a weight average molecular weight of 50,000 or more.   The composition liquid for three-dimensional modeling according to claim 1, wherein the water-soluble resin has a weight average molecular weight of 700,000 or more.   The composition liquid for three-dimensional modeling according to claim 1, wherein the water-soluble resin is polyvinylpyrrolidone.   The composition liquid for three-dimensional modeling according to any one of claims 1 to 3, wherein the crosslinking agent is a metal salt.   The composition liquid for three-dimensional modeling according to any one of claims 1 to 4, wherein the crosslinking agent is a zirconium compound.   The composition liquid for three-dimensional model | molding in any one of Claim 1 to 5 which further contains at least 1 sort (s) selected from an amino group containing compound, a phosphono group containing compound, and gluconic acid and its salt.   The composition liquid for three-dimensional modeling according to claim 6, wherein the amino group-containing compound is any one of an amino group-containing polyhydric alcohol, a hydroxyl group-containing amine compound, and an amino group-containing chelating agent.   The composition liquid for three-dimensional model | molding in any one of Claim 1 to 7 containing the said solvent and this solvent contains the water-soluble organic solvent whose vapor pressure in 100 degreeC is 10 mmHg or more.   The composition liquid for three-dimensional modeling according to any one of claims 1 to 8, wherein the organic material can be dissolved.   A three-dimensional modeling material set comprising: a three-dimensional modeling powder material including an organic material and a base material; and the three-dimensional modeling composition liquid according to claim 1.   The three-dimensional modeling material set according to claim 10, wherein the base material is coated with the organic material.   The three-dimensional modeling material set according to claim 10, wherein the base material is a base material that does not react with the three-dimensional modeling composition liquid.   The three-dimensional modeling material set according to any one of claims 10 to 12, wherein the base material is at least one of metal and ceramics.   The three-dimensional modeling material set according to any one of claims 10 to 13, wherein the organic material includes a water-soluble resin.   The three-dimensional modeling material set according to claim 14, wherein the water-soluble resin contains a modified polyvinyl alcohol resin. A powder material supply step for supplying a powder material for three-dimensional modeling including an organic material and a substrate;
A powder material curing step of applying a three-dimensional modeling composition liquid to the supplied powder material and curing a predetermined region of the powder material;
Is a manufacturing method for manufacturing a three-dimensional modeled object,
The method for producing a three-dimensional object, wherein the three-dimensional object composition liquid is the three-dimensional object composition liquid according to any one of claims 1 to 9.   The manufacturing method of the three-dimensional molded item of Claim 16 which further includes the sintering process which sinters the three-dimensional molded item produced by repeating the said powder material supply process and the said powder material hardening process. A powder material supply means for supplying a powder material for three-dimensional modeling including an organic material and a substrate;
Powder material curing means for applying the three-dimensional modeling composition liquid according to any one of claims 1 to 9 to the supplied powder material and curing a predetermined region of the powder material;
A powder material container in which the powder material for three-dimensional modeling is stored;
A curable liquid storage part in which the three-dimensional modeling composition liquid is stored;
An apparatus for producing a three-dimensional structure, characterized by comprising: